KR102498801B1 - Ethylene-alpha-olefin copolymer-triallyl phosphate composition - Google Patents

Abstract

(A) a cross-linkable ethylene/alpha-olefin copolymer, (B) an effective amount of triallyl phosphate (TAP), (C) an organic peroxide, and optionally (D) a supplemental polymer; A peroxide-curable ethylene copolymer composition, wherein the sexual ethylene/alpha-olefin copolymer is prepared by copolymerizing ethylene and an olefin-functional comonomer in the presence of a molecular catalyst useful therefor. Also provided are cured products made from the compositions, methods of making and using them, and articles containing them.

Description

Ethylene-alpha-olefin copolymer-triallyl phosphate composition

This field includes ethylene/alpha-olefin copolymer compositions, cured products made therefrom, methods of making and using them, and products containing them.

Insulated electrical/optical conductors include insulated electrical conductors, insulated conductors and insulated electro-optical conductors. Insulated conductors include coated optical fibers and fiber optic (optical) cables used in data transmission applications. Insulated electrical conductors include coated metal wires and electrical cables, including power cables used in low voltage, medium voltage, high voltage and extra high voltage transmission/distribution applications. Insulated electro-optical conductors include coated optical fibers and coated metal wires for use in data and/or power transmission applications.

Various types of wire and cable compositions are described in U.S. Patent Nos. 3,974,132; US 7,858,705 B2; WO 2007/056154; WO 2010/017553; WO 2010/017554; WO 2015/009562; WO 2016/200600 A1; PCT/US16/048014; or PCT/US16/056719.

L.L. U.S. Patent No. 3,974,132 to Valdiserri ("VALDISERRI") relates to a method for curing olefin polymers. Thermosetting ethylene polymer compositions in which triallyl phosphate is used as an adjuvant are mentioned. The composition also contains an organic peroxide “catalyst”. Examples of ethylene polymers mentioned include low density polyethylene (LDPE); ethylene copolymers having a Tg (glass transition temperature) of less than 25 degrees Celsius (° C.); or ethylene-propylene-1,4-hexadiene terpolymer. According to the discovery timeline, the catalyst used to make VALDISERRI's ethylene polymer was a Ziegler-Natta catalyst.

US Patent No. 7,858,705 B2 to JS Parent et al. ("PARENT") relates to functionalized polyolefins, wet-curable polyolefin resins, and processes for their preparation (sic) . In one aspect of Example 5, triallyl phosphate was included in the isotactic polypropylene cracking blend prior to the addition of 3-mercaptopropyl trimethoxy silane. The isotactic polypropylene, in the form of pellets, had a number average molecular weight of 50,000 and a polydispersity of 3.8.

WO 2010/017554 A1 of B. Chaudhary et al. (“CHAUDHARY”; B. Chaudhary of the present application) relates to polyolefin compositions with grafted flame retardants. CHAUDHARY includes flame retardant compositions made from or containing (a) a polyolefin and (b) a graftable phosphorus containing adjuvant. CHAUDHARY also includes a polyolefin bonded with a grafted flame retardant. (b) is present in an amount from about 1.0% to about 20.0% by weight. Suitable graftable phosphorus containing adjuvants may simultaneously contain elemental phosphorus, nitrogen and silicon. Among others, there is an example comprising a metallocene catalyzed ethylene-octene copolymer having an octene comonomer content = 7.3 mol%. Ethylene/unsaturated ester copolymers are mentioned wherein the portion of the copolymer attributable to the ester comonomer is from about 5 to about 50 weight percent, preferably from about 15 to about 40 weight percent, based on the weight of the copolymer. An example is ELVAX 265, an ethylene-vinyl acetate copolymer that is not made with molecular catalysts.

We find that the 7.3 mol% octane comonomer content of VALDISERRI's ethylene polymer, PARENT's isotactic polypropylene and CHAUDHARY's metallocene catalyzed ethylene-octene copolymer are often sufficient for use as flexible products, such as flexible electrical insulation. It was recognized that there was no flexibility. They may lack sufficient thermal or oxidation stability for use in medium to extra-high voltage power cables.

We know that conventional insulated electrical/optical conductor claddings (eg single-layer claddings or multi-layer claddings) exposed to heat for long periods of time are less flexible and prone to oxidation and embrittlement. Sufficient flexibility, thermal or oxidative stability and dielectric properties for use as single- or multi-layer sheathing on power cables, especially for medium to extra-high voltage applications, e.g. as improved cross-linked polyolefin insulation layer in multi-layer sheathing of insulated electrical/optical conductors; There is a need for new cross-linked polyolefin materials that exhibit modulus. Our challenge, then, is to improve flexibility when cured (i.e. increase), improve thermal and/or oxidative stability (increase), and/or dissipation factor that is unchanged or reduced by a factor of less than 3 (increased). It would be to formulate a new curable polyolefin composition that produces a new cross-linked polyolefin material with For thermal and/or oxidative stability properties, tensile retention elongation (TER) can be measured after thermal aging and/or oxidation induction time (OIT). After heat aging, TER is according to the procedure described below (“TER (136 ° C after 7 days)” or “TER (136 ° C after 28 days)”, collectively TER (136 ° C after 7 days or 28 days) It may be the measured tensile elongation after 7 days at 136° C. or maintained after 28 days at 136° C. Oxidation induction time may be measured in molecular oxygen atmosphere at 185° C. according to the procedure described below (“OIT(O ₂ , 185° C.)”). It can be measured at 130°C, 60 hertz (Hz) and 2 kilovolts ( kV) can be measured.

Our technical solution to this problem is a novel peroxide curable ethylene copolymer composition comprising (A) a cross-linkable ethylene/alpha-olefin copolymer, (B) an effective amount of triallyl phosphate (TAP) and (C) an organic peroxide. (composition of the present invention). (A) The cross-linkable ethylene/alpha-olefin copolymer comprises ethylene and an alpha-olefin comonomer, and optionally another comonomer selected from a non-conjugated diene and a second alpha-olefin. , prepared by a process comprising the step of copolymerizing in the presence of a molecular catalyst useful herein. Also included are novel crosslinked ethylene/alpha-olefin copolymers (crosslinked products of the present invention) prepared by curing the composition of the present invention. The cross-linked product of the present invention is sufficient and even improved (i.e. increased) for use as a single-layer coating or multi-layer coating, for example as a cross-linked polyolefin insulating layer of a multi-layer coating of insulated electrical/optical conductors. flexibility, and improved (ie, increased) thermal and oxidative stability and sufficient dielectric constant. The technical solutions of the present inventors also include methods of making and using the compositions of the present invention, and articles comprising or made from the compositions of the present invention. The compositions and cross-linked products of the present invention are useful for making cross-linked polyolefin insulating layers of single-layer coatings or multi-layer coatings, for example multi-layer coatings of insulated electrical/optical conductors. Also, crosslinks made from the composition or crosslinked product of the present invention, single or multilayer coverings (e.g., multilayer coverings containing crosslinked polyolefin insulating layers) and insulated electrical/optical conductors containing single or multiple coverings A bonded polyolefin insulating layer is included. The insulated electrical/optical conductors are useful for data and/or electrical transmission/distribution applications including low voltage, medium voltage, high response and extra high voltage applications.

The contents and summary of the invention are incorporated herein by reference. The cross-linked product of the present invention is characterized as being a TAP grafted ethylene/alpha-olefin copolymer. The copolymer is prepared by a free radical process of forming a covalent bond between the TAP molecule and (A) a cross-linkable ethylene/alpha-olefin copolymer. The free radical processes involve free radicals initiated or propagated by free radical generating compounds such as peroxides or by other means of free radical generation such as electron beam irradiation. The cross-linked product or copolymer (A) of the present invention may exhibit any gel content in the range of 0 to 100% by weight (eg as measured by decalin extraction). All flexural modulus values are measured at 23° C. unless otherwise stated.

To enable a technical solution, an effective amount of (B) TAP may be from 0.050 to less than 0.950 weight percent of (B) TAP, based on the total weight of the composition of the present invention. For example (B) TAP may be from 0.050 to 0.949%, alternatively from 0.101 to 0.901%, alternatively from 0.1501 to 0.849%, alternatively from 0.1905 to 0.8049% by weight of the composition of the present invention. The cross-linked product of the present invention obtained after curing the composition of the present invention has an improved (i.e., increased) TER (after 7 days or After 28 days, 136 °C), improved (ie, increased) OIT (O ₂ , 185 °C) and unchanged or less than 3-fold decreased (ie, <3x increased), alternatively unchanged or less than 2-fold DF (130° C., 60 Hz, 2 kV) reduced to (i.e., <2x increased). Moreover, in addition, if TAP is present in the lesser TAP-containing comparative composition in an amount greater than 0 and less than 0.050% by weight based on the total weight of the lesser TAP-containing comparative composition, then obtained after curing the less TAP-containing comparative composition Comparative crosslinked products containing less TAP than those tested had no or sufficiently improved (i.e. insufficiently increased) TER (136°C after 7 days or 28 days) for use in fusible electrical insulation for medium to high-speed power cables. ) or OIT (O ₂ , 185° C.). Further, if TAP is present in more TAP-containing comparative composition, at greater than 1.00% by weight, alternatively greater than 1.10% by weight, based on the total weight of the greater TAP-containing comparative composition, then more TAP-containing comparative composition. After curing of the composition, the more TAP comparative crosslinked product obtained has improved (or better) TER (7 days or 28 days, 136° C.), improved (or better) OIT (O ₂ , 185° C.), and It can be characterized by an enhanced (ie reduced) DF (130° C., 60 Hz, 2 kV).

Embodiment 1. (A) 58.00 to 99.90 wt% of a cross-linkable ethylene/alpha-olefin copolymer ("copolymer (A)" or "component (A)") (ethylene and alpha-olefin comonomers, and a non-conjugated diene and a second alpha-olefin, in the presence of a molecular catalyst useful therein; (B) 0.050 to 0.949% by weight of triallyl phosphate (TAP); (C) 0.050 to 5.00% by weight of an organic peroxide; and (D) 0.00 to 40 wt %, alternatively 0.00 to 20 wt %, alternatively 0.00 wt %, alternatively > 0.00 to 10 wt % (ethylene/unsaturated carboxylic acid ester copolymer, polyethylene homopolymer, A peroxide-curable ethylene copolymer composition comprising a non-(molecular catalyst) type ethylene/alpha-olefin copolymer and a propylene-based polymer selected from 80.00 to 99.90% by weight of the total weight of components (A) and (D); alternatively 90.0 to 99.90 weight percent, alternatively 90.0 to 96.5 weight percent; all weight percent based on the total weight of the peroxide curable ethylene copolymer composition, wherein the total weight of the peroxide curable ethylene copolymer composition is 100.0 % by weight). In some embodiments, when the sum of the weight percents of components (A) to (C), alternatively (A) to (D), is less than 100.00 weight percent, the composition comprises at least one additional It further contains at least one or more of component (D) or component (E) - (O). Typically, the step (A) copolymerizing ethylene and an alpha-olefin comonomer and another comonomer selected from a non-conjugated diene and a second alpha-olefin to produce a cross-linkable ethylene/alpha-olefin copolymer comprises: This is done in the absence of a Ziegler-Natta catalyst.

Aspect 2. The peroxide curable ethylene copolymer composition of Aspect 1, further described by any one of the following limitations (i) to (ii): (i) wherein the alpha-olefin comonomer is (C ₃ -C ₂₀ ) an alpha-olefin, wherein the (A) ethylene/alpha-olefin copolymer is characterized by at least one, alternatively two, alternatively each of the following properties (a) through (c): (C ₃ -C ₂₀ ) is an alpha-olefin copolymer (eg, a binary polymer copolymerizing without other comonomers or a terpolymer copolymerizing with a second alpha-olefin comonomer) (according to (a1) ASTM D790-15e2 a measured flexural modulus of > 0 to 40,000 psi (> 0 to 278 MPa), alternatively > 0 to 6,500 psi (> 0 to 45 MPa), alternatively > 0 to 5,000 psi (> 0 to 34 MPa) 2% sec) and/or (a2) a density of from 0.850 to 0.930 grams per cubic centimeter (g/cm ³ ), alternatively from 0.850 to 0.890 g/cm ³ measured according to ASTM D792, (b) ASTM 3418- A glass transition temperature (Tg) of -130 to -20 °C measured by differential scanning calorimetry (DSC) according to 15, and (c) of 0.5 decigrams per minute (dg/minute) measured according to ASTM D1238-04 ~50 dg/min of melt index (190°C, 2.16 kilograms (kg), "I ₂ "); or (ii) wherein the alpha-olefin comonomer is propylene and another comonomer is used but non-conjugated (C ₆ -C ₂₀ )diene, wherein the (A) crosslinkable ethylene/alpha-olefin copolymer is characterized by at least one, alternatively both, alternatively each of the following properties (a) through (d): ( _a1 ) > 0 to 20,000 psi (> 0 to ₁₃₈ MPa) measured according to ASTM D790-15e2; , alternatively > 0 to 6, 500 psi (> 0 to 45 MPa), alternatively > 0 to 5,000 psi (> 0 to 34 MPa) of flexural modulus (2% sec) and/or (a2) 0.850 to 0.910 cubic meter measured according to ASTM D792 Density in grams per centimeter (g/cm ³ ), alternatively from 0.850 to 0.890 g/cm ³ , (b) from -130 to -20 °C as measured by differential scanning calorimetry (DSC) according to ASTM 3418-15. glass transition temperature (Tg), (c) a melt index of 0.1 decigrams per minute (dg/min) to 50 dg/min (190° C., 2.16 kilograms (kg), “I ₂ ” measured according to ASTM D1238-04); ), and (d) a Mooney viscosity of 15 to 170 (ML1 + 4 at 125° C.) measured according to ASTM D1646-15 (1 min warm-up time and 4 min rotor run time). In some embodiments, the copolymer (A) is free of covalently bonded silicon atoms. In another embodiment, the copolymer (A) further contains a hydrolyzable silyl functional group (eg, a trimethoxysilyl group), and the copolymer (A) is an ethylene/alpha-olefin/olefin functional hydrolyzable silane copolymer It is characterized by being a chain. The ethylene/alpha-olefin/olefin functional hydrolysable silane copolymer can be prepared as described below.

Aspect 3. The peroxide curable ethylene copolymer composition of Aspect 1 or Aspect 2, further described by any one of the limitations (i) to (iv): (i) wherein (A) cross-linkable ethylene/alpha- wherein the olefin copolymer is from 90 to 99%, alternatively from 91 to 98%, alternatively from 93 to 97% by weight of the peroxide-curable ethylene copolymer, and the peroxide-curable ethylene copolymer composition is supplemented with (D) above does not contain polymers (deficient); (ii) the (A) crosslinkable ethylene/alpha-olefin copolymer is from 58.00 to 90.00%, alternatively from 80.0 to 90.0%, alternatively from 85.0 to 90.0% by weight of the peroxide-curable ethylene copolymer composition; the (D) supplemental polymers are each from 40.0 to 1.0%, alternatively from 10.0 to 1.0%, alternatively from 10.0 to 7.0% by weight of the peroxide-curable ethylene copolymer composition; (iii) said (D) supplemental polymer is present and is a polypropylene homopolymer; and (iv) are both (ii) and (iii). All weight percentages are based on the total weight of the peroxide-curable ethylene copolymer composition.

Aspect 4. The peroxide curable ethylene copolymer composition of any one of Aspects 1-3, further described by any one of the limitations (i)-(iv): (i) above (B) triallyl phosphate (TAP) is 0.090 to 0.940 wt %; (ii) 0.100 to 0.900% by weight of (B) triallyl phosphate (TAP); (iii) 0.19 to 0.849 weight percent of (B) triallyl phosphate (TAP); (iv) 0.200 to 0.800 weight percent of (B) triallyl phosphate (TAP); All weight percentages herein are based on the total weight of the peroxide-curable ethylene copolymer composition.

Aspect 5. The peroxide-curable ethylene copolymer composition of any one of Aspects 1-4, further described by any one of the limitations (i) through (v): (i) the organic peroxide of (C) above 1.0 to 4.0 weight percent, alternatively 1.5 to 3.0 weight percent, alternatively 1.9 to 2.4 weight percent, based on the total weight of the peroxide-curable ethylene copolymer composition; (ii) the (C) organic peroxide is a compound of formula R ^{O -OO-RO (each R O is} independently a (C ₁ -C ₂₀ ) alkyl group or a (C ₆ -C ₂₀ ) aryl group); (iii) the (C) organic peroxide is bis(1,1-dimethylethyl) peroxide; bis(1,1-dimethyl propyl) peroxide; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexane; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexyne; 4,4-bis(1,1-dimethylethylperoxy)valeric acid; butyl ester; 1,1-bis(1,1-dimethylethylperoxy)-3,3,5-trimethylcyclohexane; benzoyl peroxide; tert-butyl peroxybenzoate; di-tert-amyl peroxide (“DTAP”); bis(alpha-t-butyl-peroxyisopropyl) benzene ("BIPB"); isopropylcumyl t-butyl peroxide; t-butylcumyl peroxide; di-t-butyl peroxide; 2,5-bis(t-butylperoxy)-2,5-dimethylhexane; 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne-3,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; isopropylcumyl cumyl peroxide; butyl 4,4-di(tert-butylperoxy)valerate; or di(isopropylcumyl) peroxide; or dicumyl peroxide; (iv) said (C) organic peroxide is dicumyl peroxide; and (v) a combination of any of (i) and (ii) to (iv).

Aspect 6. The peroxide curable ethylene copolymer composition of any one of Aspects 1 through 5, further described by the following limitation (i) or (ii): (i) the total amount of components (A) through (D) is 100% by weight of it; or (ii) the total amount of components (A) to (D) is less than 100% by weight, and the peroxide-curable ethylene copolymer composition further comprises at least one of components (E) to (O) (E). antioxidants; (F) an adjuvant other than TAP; (G) polydimethylsiloxane (PDMS) fluid; (H) hindered amine stabilizers; (I) flame retardants; (J) tree retardants; (K) colorants; (L) liquid aromatic or saturated hydrocarbons (LASH); (M) methyl radical scavengers; (N) scorch retardants; and (O) fillers). In some embodiments, the peroxide-curable ethylene copolymer composition each further comprises one or more of (E) an antioxidant, (F) an adjuvant other than TAP, (H) a hindered amine stabilizer, and (J) a tree retardant. . In some embodiments, the peroxide-curable ethylene copolymer composition comprises components (G) a PDMS fluid, (I) a flame retardant, (K) a colorant, (L) a liquid aromatic or saturated hydrocarbon (LASH); (M) methyl radical scavengers; (N) scorch retardants; and (0) a filler, alternatively no further comprising each of these.

Embodiment 7. The peroxide curable ethylene copolymer composition of embodiment 6, further described by any one of the following limitations (i) to (vi): (i) wherein the peroxide-curable ethylene copolymer composition comprises component (E) Further comprising an antioxidant, wherein the (E) antioxidant is bis(4-(1-methyl-1-phenylethyl)phenyl)amine; 2,2'-methylene-bis(4-methyl-6-t-butylphenol); 2,2'-thiobis(2-t-butyl-5-methyl phenol); 2,2'-thiobis(6-t-butyl-4-methylphenol; tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-tri Azine-2,4,6-trione; Pentaerythritol tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate; 3,5-bis(1 ,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2'-thiodiethanediyl ester; or distearyl thiodipropionate; (ii) the peroxide-curable ethylene copolymer composition comprising TAP Further comprising an adjuvant component (F) other than TAP, wherein the adjuvant (F) other than TAP is triallyl isocyanurate (TAIC); triallyl phosphate triamide, N-hydroxymethyl-3-dimethyl phosphonopropionamide , an unsaturated organic phosphorus compound such as 2-ethyl-methacrylic acid phosphoric acid, a phosphoric acid ester of hydroxy ethyl methacrylic acid, or vinyl phosphonic acid; or alpha-methyl styrene dimer (AMSD) or diisopropenylbenzene (DIPB) (iii) the peroxide-curable ethylene copolymer composition further comprises a component (H) hindered amine stabilizer, wherein the (H) hindered amine stabilizer is 1,3,5-triazine-2,4; 6-triamine, N2,N2″-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidi Nyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N', N"-dibutyl-N',N"-bis(1,2,2,6,6- (iv) the peroxide curable ethylene copolymer composition further comprises component (J) a tree retardant, wherein (J) the tree retardant has a number average of 10,000 to 30,000 g/mol is poly(ethylene glycol) (PEG) having a molecular weight (Mn); (v) the peroxide curable ethylene copolymer composition further comprises a combination of limitations (i) to (iv); and (vi) the peroxide curable ethylene copolymer composition. The ethylene copolymer composition comprises 0.20 to 0.50% by weight of component (E) (wherein (E) is 2,2'-thiobis(2-t-butyl-5-methylphenol)), 0.30 to 0.50% by weight of component (F) (wherein (F) is alpha-methyl styrene dimer (AMSD)), 0.10 to 0.30% by weight of component (H) (wherein (H) is 1,3,5-triazine-2,4, 6-triamine, N2,N2″-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperylic Dinyl) amino] -1,3,5-triazin-2-yl] amino] propyl] -N', N"-dibutyl-N', N"-bis (1,2,2,6,6- pentamethyl-4-piperidinyl)-, and 0.40 to 0.80% by weight of component (J), wherein (J) is PEG having an Mn of 15000 to 25000 g/mol.

Embodiment 8. The method according to any one of Embodiments 1 to 7, wherein the crosslinkable ethylene/alpha-olefin copolymer (A) is an ethylene/propylene/diene terpolymer, and wherein the diene is 5-ethylidene-2-nor A peroxide-curable ethylene copolymer composition that is bornene.

Aspect 9. A process for preparing the peroxide-curable ethylene copolymer composition according to any one of Aspects 1-8, wherein the process comprises effective amounts of components (A) through (C) and optional optional components (D) through (O). ) to produce the peroxide-curable ethylene copolymer composition. In some embodiments, the method is performed according to Manufacturing Method 1 described hereinafter.

Embodiment 10. The method of embodiment 9, wherein the contacting step comprises internal mixing of components (A) to (C) and optional components (D) to (O) or components (B), (C) and any optional components (D) to (O). immersing at least one of components (D) to (O) into component (A). Immersion is a passive method without agitation like melt mixing.

Aspect 11. A cross-linked ethylene/alpha-olefin copolymer product that is the product of curing the peroxide-curable ethylene copolymer composition of any one of Aspects 1-8.

Aspect 12. The method of Embodiment 11, wherein (A) the cross-linkable ethylene/alpha-olefin copolymer is an ethylene/propylene/diene terpolymer, the diene is 5-ethylidene-2-norbornene, and the cross-linkable An ethylene/alpha-olefin copolymer product having a tensile elongation of 30% to 90% after heating at 180°C in an oven for 17 hours and a tensile elongation of 25% to 80% after heating at 180°C in an oven for 24 hours. Phosphorus cross-linked ethylene/alpha-olefin copolymer product.

Aspect 13. A manufactured article comprising a shaped form of a cross-linked ethylene/alpha-olefin copolymer product of type 11 or 12.

Aspect 14. A coated conductor comprising a conductive core and an insulating layer at least partially covering the conductive core, wherein at least a portion of the insulating layer is the cross-linked ethylene/alpha-olefin copolymer product of Embodiment 11 or Embodiment 12 A coated conductor comprising a. The insulating layer may be a single-layer covering material or a multi-layer covering material covering the conductive core. The coated conductor is as generally described in the introduction incorporated herein by reference, except that the crosslinked polyolefin insulating layer of the multilayer covering of the insulated electrical/optical conductor comprises the crosslinked material of the present invention. It may be an insulated electrical/optical conductor such as The insulated electrical/optical conductors of the present invention may be insulated electrical conductors and may be useful for transmitting electricity.

Aspect 15. A method of conducting electricity, wherein the method comprises applying a voltage across the conductive core of the coated conductor of aspect 14 to cause a flow of electricity through the conductive core.

The above peroxide-curable ethylene copolymer composition (eg, the inventive composition of Aspects 1-7). The total weight of all constituents is 100% by weight. The composition of the present invention is substantially free of component (A) or polyolefins other than components (A) and (D), and alternatively free of them. For example, it is substantially free of, or alternatively free of, ethylene/unsaturated carboxylic acid ester copolymers, poly(C ₄ -C ₄₀ )alpha-olefin homopolymers, or polystyrene. Otherwise, the composition of the present invention may comprise additional polymers, provided that any additional polymers do not disprove a technical solution. In this context, 'consisting essentially of' means that the composition of the present invention contains 0 to 1 weight percent, alternatively 0 to <0.1 weight percent, of any other polymer, excluding components (A) to (O). %, alternatively 0% by weight.

The peroxide-curable ethylene copolymer composition contains components (A) to (C) described in more detail below. The peroxide-curable ethylene copolymer composition contains (A) a cross-linkable ethylene/alpha-olefin copolymer, which is a cross-linkable macromolecule having ethylene-derived monomer units and alpha-olefin-derived comonomer units. (A) may consist of carbon atoms and hydrogen atoms, and optionally silicon atoms and silicon-bonded oxygen atoms. (A) may be substantially or substantially free of other heteroatoms (eg, halogen, N, S, P). Under curing conditions (which typically involve heating to a temperature above 160° C., alternatively above 180° C.), (C) the organic peroxide forms oxygen-radicals. O-radicals (A) extract oxygen atoms from internal carbon atoms in the backbone or side chains of cross-linkable ethylene/alpha-olefin copolymers, thereby generating radicals with no internal polymeric chains on the carbon atoms. . The carbon radicals couple to form a cross-linked ethylene/alpha-olefin copolymer. Cross-linking occurs through a curing reaction under curing conditions, thereby forming a networked polymer, a cross-linked ethylene/alpha-olefin copolymer.

The peroxide-curable ethylene copolymer composition may be a one-part formulation, alternatively a two-part formulation, alternatively a three-part formulation. One-part formulations include components (A) through (C) and optional components such as components (D) through (O) in a single mixture, which is a peroxide curable ethylene copolymer composition. The two-part formulation may comprise a first part and a second part, wherein the first part consists essentially of (A) a cross-linkable ethylene-vinyl acetate copolymer and optionally (D) a supplemental polymer; Two parts consists essentially of a further masterbatch composition containing at least one of components (B) to (C), and optional additives such as additives (D) to (O). Any optional components such as the remaining components (B) to (C) and additives (D) to (O) may be present in the first part, the second part, or both. The peroxide-curable ethylene copolymer composition may be prepared from a two-part formulation by combining a first part and a second part to provide a mixture thereof to the peroxide-curable ethylene copolymer composition. A three-part formulation can be the same as a two-part formulation, except that component (C) and, optionally, any (G) PDMS fluid are not present in the first or second part, but component (C) organic peroxide , and optionally component (G) PDMS fluid comprises the third part. When (C) and, optionally, (G) comprises a third part, the peroxide-curable ethylene copolymer composition is obtained by combining the first part and the second part to form components (A), (B), any ( D) and optionally a mixture thereof containing optional components (H) to (O); If desired, optionally pelletizing the mixture to provide the mixture in pellet form; The mixture (e.g., pellets) of the first and second parts is then contacted with a third part (i.e., (C) organic peroxide and optionally (G) PDMS fluid) to form a peroxide-curable ethylene copolymer composition It can be prepared by providing. Generally, the combination or mixing (contacting) of components (A) to (C), and optionally (D), and any optional components such as additives (E) to (O), is performed at a temperature of about 20° C. to 100° C. temperature for 2 to 100 hours, for example, at a temperature of 50° C. to 80° C. for 6 to 24 hours. Higher temperatures may be used when combining components (A), (B), optionally (D) and optional components (E) to (O) to produce a mixture in the absence of (C) organic peroxides; , then the mixture may be cooled to a temperature below the curing temperature prior to being combined with or contacted with (C) the organic peroxide. Any combination of components (A) through (C) and optionally (D), and optional optional components (D) through (O) may be used as the first part or second part of a one-part formulation, or a two-part formulation. There is no intrinsic cause for why In general, there is no incompatibility between (A) and (O).

In some embodiments, (A) the cross-linkable ethylene/alpha-olefin copolymer of any one of embodiments (i) to (i) of Embodiment 2 is the same as any one of embodiments (i) to (ii) above. Characterized in that the copolymer (A) is a hydrolysable silane-grafted cross-linkable ethylene/alpha-olefin copolymer prepared by post-reactor grafting of an olefin functional hydrolysable silane (e.g., vinyl trimethoxysilane) onto the copolymer (A). have

In some embodiments, (A) the crosslinkable ethylene/alpha-olefin copolymer of any one of embodiments (i) to (ii) of aspect 2 has at least one of the following properties (a) to (c), alternatively Optionally two, alternatively each characterized by: (a1) 500 to 40,000 psi (3 to 276 MPa), alternatively 500 to 20,000 psi (3 to 138 MPa) measured according to ASTM D790-15e2, alternatively 500 to 6,500 psi (3 to 45 MPa), alternatively 500 to 4,501 psi (3 to 31 MPa), alternatively 500 to 4001 psi (3 to 28 MPa), alternatively 500 to 3501 psi (3 to 24 MPa), alternatively a flexural modulus (2% sec) of 900 to 2010 psi (6 to 14 MPa) and/or (a2) 0.850 to 0.930 g/cm ³ measured according to ASTM D792, alternatively 0.850 to 0.910 g/cm ³ , alternatively 0.850 to 0.890 g/cm ³ , alternatively 0.850 to 0.885 g/cm ³ , alternatively 0.850 to 0.880 g/cm ³ , alternatively 0.850 to 0.875 g/cm ³ , alternatively a density of 0.870 to 0.875 g/cm ³ ; (b) a Tg of -120 to -30 °C, alternatively -110 to -50 °C as measured by DSC according to ASTM 3418-15; (c) a melt index (190° C., 2.16 kilograms (kg), “I ₂ ”) of from 0.3 to 30 dg/min, alternatively from 0.5 to 20.0 dg/min, measured according to ASTM D1238-04. In some embodiments, (A) the crosslinkable ethylene/alpha-olefin copolymer of any one of embodiments (i) to (ii) is further cured (in the absence of TAP) with dicumyl peroxide to form DF (e) a comparative crosslinked ethylene/alpha-olefin copolymer without TAP having greater than 0.1%, alternatively greater than 0.3%, alternatively greater than 0.5% (130° C., 60 Hz, 2 kV) has a characteristic In some embodiments, (A) is characteristic (a1); alternatively characteristic (a2); alternatively characteristic (b); alternatively characteristic (c); alternatively properties (a1) and (a2); alternatively properties (a1) or (a2) and (b); alternatively features (a1) or (a2) and (c); alternatively characterized by properties (a1), (a2), (b) and (c).

Component (A): cross-linkable ethylene/alpha-olefin copolymer. A “copolymer” is a macromolecule or macromolecule having monomer units prepared by polymerizing monomers and one or more different types of comonomer units prepared by polymerizing one or more different alpha-olefin comonomers and optionally non-conjugated dienes. is an aggregation of Monomers and comonomers are polymerizable molecules. A monomer unit, also called a "mer", is the largest constituent unit from which a single monomer molecule contributes (derives) to the structure of a macromolecule. A comonomer unit is the largest constituent unit from which one comonomer molecule contributes (derives) to the structure of a macromolecule. Each unit is usually divalent. A "bipolymer" is a copolymer composed of a monomer and one comonomer. A “terpolymer” is a copolymer made of a monomer and two different comonomers. "Ethylene/alpha-olefin copolymer" is an ethylene/alpha-olefin copolymer wherein the monomer units are derived from the monomer ethylene (CH ₂ =CH ₂ ) and comprise an average of at least 50% by weight macromolecules per molecule, and the comonomer units are at least one alpha-olefin comonomer and, optionally, a copolymer derived from a second alpha-olefin comonomer or non-conjugated (C ₆ -C ₂₀ ) diene. Each comonomer can independently have hydrogen atoms and 3 to 20 carbon atoms per molecule. The (A) cross-linkable ethylene/alpha-olefin copolymer may be granules or pellets in bulk form.

In some of the above embodiments, the alpha-olefin comonomer is a (C ₃ -C ₂₀ )alpha-olefin, alternatively a (C ₄ -C ₂₀ )alpha-olefin, alternatively a (C ₄ -C ₈ )alpha-olefin can be The (A) cross-linkable ethylene/alpha-olefin copolymer may be a corresponding ethylene-(C ₃ -C ₂₀ )alpha-olefin copolymer (eg, a di- or terpolymer), each of which is independently characterized by at least one, alternatively two, alternatively each of the characteristics (a) to (c), and optionally (e). Ethylene-(C ₃ -C ₂₀ )alpha-olefin dipolymers consist essentially of ethylene-derived monomer units and (C ₃ -C ₂₀ ) alpha-olefin-derived comonomer units. The ethylene-(C ₃ -C ₂₀ ) alpha-olefin terpolymer consists essentially of ethylene-derived monomer units, a first (C ₃ -C ₂₀ ) alpha-olefin-derived comonomer unit and a second (C ₃ -C ₂₀ ) It consists of alpha-olefin-derived comonomer units. The first (C ₃ -C ₂₀ ) alpha-olefin-derived comonomer unit is derived from a first (C ₃ -C ₂₀ ) alpha-olefin and the second (C ₃ -C ₂₀ ) alpha-olefin-derived comonomer unit The unit is derived from a second (C ₃ -C ₂₀ ) alpha-olefin, wherein the first and second (C ₃ -C ₂₀ ) alpha-olefins are different (e.g., the first (C ₃ -C ₂₀ ) alpha-olefin is propylene and the second (C ₃ -C ₂₀ ) alpha-olefin is 1-hexene). The ethylene monomer units may be 99 to 51 weight percent, alternatively 95 to 60 weight percent, alternatively 90 to 70 weight percent of the ethylene-(C ₃ -C ₂₀ ) alpha-olefin dipolymer, or a single thereof It may be a single point permutation, such as 99 to 70 wt% or 90 to 60 wt%. The (C ₃ -C ₂₀ )alpha-olefin comonomer unit is present in an amount of 1 to 49%, alternatively 5 to 40%, alternatively 10 to 40% by weight of the ethylene-(C ₃ -C ₂₀ )alpha-olefin binary polymer. 30 wt%, or a single point permutation, such as 1 to 30 wt% or 10 to 40 wt%. Weight percent values are averages per molecule of ethylene-(C ₃ -C ₂₀ ) alpha-olefin binary polymer. Alpha-olefin comonomers contain one carbon-carbon double bond (C = C), which is located at the terminal carbon atom. The (C ₃ -C ₂₀ ) alpha-olefin may be a (C ₄ -C ₈ ) alpha-olefin, and the ethylene-(C ₃ -C ₂₀ ) alpha-olefin copolymer has the following properties (a) to (c) and _{optionally at} least one, alternatively two or alternatively each of (e). (C ₃ -C ₂₀ ) alpha-olefins may be linear, branched or cyclic-containing. In some embodiments, a (C ₃ -C ₂₀ ) alpha-olefin is a (C ₃ -C ₁₀ ) alpha-olefin, alternatively a (C ₄ -C ₈ )alpha-olefin, alternatively (C ₁₀ -C ₂₀ ) It is an alpha-olefin. Examples of suitable (C ₃ -C ₂₀ ) alpha-olefins include propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, These are 1-tetradecene, 1-hexadecene, and 1-octadecene. (C ₃ -C ₂₀ ) alpha-olefins are unsubstituted or substituted with cycloalkyl groups on saturated (sp3) carbon atoms such as 3-cyclohexyl-1-propene and vinylcyclohexane. Examples of ethylene-(C ₃ -C ₂₀ ) alpha-olefin binary polymers are ethylene/propylene binary polymers, ethylene/1-butene binary polymers, ethylene/1 hexene binary polymers, and ethylene/1-octene binary polymers. Examples of ethylene-(C ₃ -C ₂₀ ) alpha-olefin terpolymers are ethylene/propylene/1-octene terpolymers, ethylene/propylene/1-butene terpolymers and ethylene/1-butene/1-octene terpolymers. The ethylene-(C ₃ -C ₂₀ ) alpha-olefin copolymer may be an ethylene-(1-octene) binary polymer. An example of a suitable ethylene-(C ₃ -C ₂₀ ) alpha-olefin copolymer has a density of 0.872 g/cm ³ measured according to ASTM D792; a melt index (190° C., 2.16 kg) of 4.8 g/10 min measured according to ASTM D1238; flexural modulus (2% sec) of 1570 psi (10.8 MPa) measured according to ASTM D790-15e2; and a glass transition temperature (Tg) of -53°C as measured by differential scanning calorimetry (DSC) according to ASTM 3418-15; Developmental XUS 38660.00 Polyolefin Elastomer by The Dow Chemical Company is an ethylene-1-octene copolymer prepared with a molecular catalyst obtained commercially.

In some of the above embodiments, (A) the comonomer used to prepare the cross-linkable ethylene/alpha-olefin copolymer may be a combination of propylene and a non-conjugated (C ₆ -C ₂₀ ) diene, and (A) the cross-linkable The sex ethylene/alpha-olefin copolymer is an ethylene-propylene-(C ₄ -C ₂₀ ) diene terpolymer (EPDM). EPDM consists essentially of ethylene-derived monomer units, propylene-derived comonomer units and non-conjugated (C ₆ -C ₂₀ ) diene-derived comonomer units. The ethylene monomer units may be 99 to 51 wt %, alternatively 95 to 60 wt %, or 90 to 70 wt % of the EPDM, or a single point permutation thereof, such as 99 to 70 wt % or 90 to 60 wt %. . Ethylenic monomer unit weight percent may be determined according to ASTM D3900. (C ₃ -C ₂₀ ) alpha-olefin comonomer units may be from 1 to 48.1 weight percent of the EPDM, alternatively from 5 to 39.1 weight percent, alternatively 10 to 29.1 wt%, or single point permutations thereof, such as 1 to 39.1 wt% or 10 to 48.1 wt%. The non-conjugated (C ₆ -C ₂₀ ) diene may be 0.1 to 10.0%, alternatively 0.2 to 5.0%, alternatively 0.3 to 3.0% by weight of the EPDM. Weight percent values are averages per molecule of EPDM. The total weight of ethylene, propylene and non-conjugated (C ₆ -C ₂₀ ) diene units is 100% by weight of EPDM. Non-conjugated (C ₆ -C ₂₀ ) dienes contain only two carbon-carbon double bonds. (C ₄ -C ₂₀ ) C = C of diene is non-conjugated. In some embodiments, the non-conjugated (C ₆ -C ₂₀ ) diene is a non-conjugated (C ₆ -C ₁₅ ) diene, alternatively a non-conjugated (C ₆ -C ₈ ) diene. Examples of suitable non-conjugated (C ₆ -C ₂₀ ) dienes include 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene; branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene; single ring cycloaliphatic dienes such as 1,3-cyclopentadiene, 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene; and multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, and bicyclo-(2,2,1)-hepta-2,5- dienes; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene , and norbornadiene. In some embodiments, the (C ₆ -C ₂₀ ) diene is 1,4-hexadiene (“HD”), 5-ethylidene-2-norbornene (“ENB”), 5-vinylidene-2-norbornene ene (“VNB”), 5-methylene-2-norbornene (“MNB”) or dicyclopentadiene (“DCPD”). In another embodiment, the non-conjugated (C ₆ -C ₂₀ ) diene is 1,4-hexadiene or 1,7-octadiene. The non-conjugated (C ₆ -C ₂₀ ) diene may be 1,4-hexadiene, 1,6-hexadiene, dicyclopentadiene, ethylidene norbornene or vinyl norbornene; and (A) the cross-linkable ethylene/alpha-olefin terpolymer is ethylene characterized by at least one, alternatively two or alternatively each of the properties (a) to (d), and optionally (e). -Propylene-1,4-butadiene terpolymer; an ethylene-propylene-1,4-hexadiene terpolymer characterized by at least one, alternatively two or alternatively each of the properties (a) to (d), and optionally (e); an ethylene-propylene-1,6-hexadiene terpolymer characterized by at least one, alternatively two or alternatively each of the properties (a) to (d), and optionally (e); an ethylene-propylene-dicyclopentadiene terpolymer characterized by at least one, alternatively two or alternatively each of the properties (a) to (d), and optionally (e); an ethylene-propylene-ethylidene norbornene terpolymer characterized by at least one, alternatively two or alternatively each of the properties (a) to (d), and optionally (e); or an ethylene-propylene-vinyl norbornene terpolymer characterized by at least one, alternatively two or alternatively each of the properties (a) to (d), and optionally (e). An example of a suitable EPDM has an ethylenic monomer content of 72.0% by weight and a melt index (190° C., 2.16 kg) of 1.0 g/10 min, prepared using a molecular catalyst and measured according to D3900B of ASTM; an ethylene-propylene-diene terpolymer purchased as VISTALON EPDM, such as VISTALON 722 from ExxonMobil; The diene may be 1,4-hexadiene, VNB or ENB. Other examples of EPDM are prepared using molecular catalysts; Commercially obtained as NORDEL IP EPDMs from The Dow Chemical Company, such as NORDEL IP 3722P EL hydrocarbon rubber, is an ethylene-propylene-diene terpolymer having an ethylenic monomer unit level of 71 weight percent and an ENB comonomer unit level of less than 1 weight percent. . ENB weight percent can be determined according to ASTM D6047.

In some embodiments, (A) the cross-linkable ethylene/alpha-olefin copolymer or (D) the comonomer used to make the supplemental polymer is described in WO2016/200600 A1 of Chaudhary (PCT/US16 filed May 24, 2016). /033879); or an olefin functional hydrolysable silane such as the hydrolysable silane monomers of paragraph [0019] of U.S. Patent No. 5,266,627 to Meverden et al. The olefin functional hydrolysable silane can be grafted (post-reactor) onto the copolymer (A) or to the supplemental polymer (D). Alternatively, (A) the olefin-functional hydrolysable silane is copolymerized with ethylene, an alpha-olefin and, optionally, a second comonomer such as a second alpha-olefin or non-conjugated diene to contain a hydrolysable silyl group; Cross-linkable ethylene/alpha-olefin copolymers can be prepared directly. Alternatively, an olefin functional hydrolysable silane can be copolymerized with ethylene and an unsaturated carboxylic ester comonomer to directly prepare (D) a cross-linkable ethylene/unsaturated carboxylic ester copolymer containing hydrolysable silyl groups. In some embodiments, the olefin functional hydrolysable silane is vinyltrimethoxysilane (VTMS), vinyltriethoxysilane (VTES), vinyl triacetoxysilane or gamma-(meth)acryloxypropyl trimethoxy silane; The hydrolysable silyl group is 2-trimethoxysilylethyl, 2-triethoxysilylethyl, 2-triacetoxysilylethyl, or 3-trimethoxysilyl propyloxycarbonylethyl or 3-trimethoxysilylpropyloxy It is carbonylpropyl.

(A) Other embodiments of cross-linkable ethylene/alpha-olefin copolymers, the properties and amounts of which have been previously described and hereinafter exemplified in the Examples of the present invention. (A) cross-linkable ethylene/alpha-olefin copolymers having at least one, alternatively two, alternatively each, and optionally (e) of properties (a) to (d) are generally known. Copolymers may be obtained from commercial suppliers such as The Dow Chemical Company, or prepared by copolymerizing ethylene and one or more olefin-functional comonomers, with or without catalysts.

Polymerization methods suitable for preparing (A) cross-linkable ethylene/alpha-olefin copolymers and (D) supplemental polymers are generally well known. For example, a cross-linkable ethylene/alpha-olefin copolymer is formed by copolymerizing ethylene and one or more olefin-functional comonomers at low pressure (e.g., with a catalyst) or high pressure (e.g., without a catalyst) in a reactor (A ) can produce cross-linkable ethylene/alpha-olefin copolymers. Alternatively, the (A) cross-linkable ethylene/alpha-olefin copolymer is prepared by a post-reactor graft process such as reactive extrusion of polyethylene with a comonomer such as an olefin functional hydrolyzable silane (optionally with a peroxide or catalyst). (A) cross-linkable ethylene/alpha-olefin copolymers in the form of graft copolymers. (D) Supplementary polymers, particularly ethylenic polymers, can be prepared in a similar manner.

Component (B): Triallyl Phosphate, TAP, is a compound of formula O=P(OCH ₂ C(H)=CH ₂ ) ₃ . it is commercially available (B) An embodiment of TAP and its amount have been described above and exemplified later in the Examples of the present invention.

Ingredient (C): Organic peroxides. (C) the organic peroxide may be 0.05 to 4.5%, alternatively 0.1 to 3%, alternatively 0.5 to 2.5% by weight of the peroxide-curable ethylene copolymer composition. The (C) organic peroxide may be represented by the formula R ^O -OOR ^O , wherein each R ^O is independently a (C ₁ ~ C ₂₀ ) alkyl group or a (C ₆ ~ C ₂₀ ) aryl group. Each (C ₁ -C ₂₀ )alkyl group is independently unsubstituted or substituted with one or two (C ₆ -C ₁₂ )aryl groups. Each (C ₆ ~C ₂₀ )aryl group is unsubstituted or substituted with 1 to 4 (C ₁ -C ₁₀ )alkyl groups. The (C) organic peroxide may be any one of the organic peroxides described above, or a combination of two or more thereof. In some embodiments, only a single type of (C) organic peroxide, e.g., a 20:80 (wt/wt) blend of t-butyl cumyl peroxide and bis(t-butyl peroxy isopropyl)benzene (e.g., LUPEROX D446B commercially available from Arkema), alternatively dicumyl peroxide (eg PERKADOX BC-FF available from AkzoNobel) is used.

Optional component (D) supplemental polymer selected from ethylene/unsaturated carboxylic acid ester copolymers, polyethylene homopolymers, non(molecular catalyst)-formed ethylene/alpha olefin copolymers and propylene-based polymers. Polyethylene homopolymers are made up of ethylene monomer units. The non(molecular catalyst)-formed ethylene/alpha-olefin copolymer comprises ethylene monomer units and olefin comonomer units. In some embodiments, the non(molecular catalyst)-formed ethylene/alpha-olefin copolymer is prepared by copolymerizing ethylene and an alpha-olefin in the presence of a Ziegler-Natta catalyst, or without any catalyst, as in high pressure polymerization. . The polyethylene homopolymer or non-(molecular catalyst)-formed ethylene/alpha-olefin copolymer has no covalently bonded silicon atoms, alternatively the polyethylene homopolymer or non-(molecular catalyst)-formed ethylene/alpha-olefin copolymer has: It may additionally contain a hydrolysable silyl functional group (eg, a trimethoxysilyl group), which may be prepared as described herein. A "propylene-based polymer" is a polypropylene homopolymer having only repeating units derived from the monomer propylene (CH ₃ CH ₂ =CH ₂ ), or a homopolymer comprising monomer units derived from the monomer propylene (CH ₃ CH ₂ =CH ₂ ) and one or more olefins. It is a propylene-based copolymer having one or more comonomer units derived from -functional comonomers. The propylene monomer units comprise, on average per molecule, at least 50% by weight of the macromolecules of the propylene-based copolymer. The comonomer units are independently derived from one or more olefin-functional comonomers previously described for ethylene/alpha-olefin copolymers. In some embodiments, the olefin-functional comonomer(s) used to prepare the comonomer units of the propylene-based copolymer are the (C ₃ -C ₂₀ ) alpha-olefins mentioned above and incorporated herein by reference.

In some embodiments, (D) the supplemental polymer is absent from the peroxide curable ethylenic copolymer composition, and thus is absent from the cross-linked product of the present invention made therefrom. In some embodiments, (D) is present in a peroxide-curable ethylene copolymer composition and (D) is an ethylene/unsaturated carboxylic acid ester copolymer, alternatively (D) is a polyethylene homopolymer; alternatively (D) is a non(molecular catalyst)-formed ethylene/alpha-olefin copolymer; Alternatively (D) is a propylene-based polymer. Ethylene/unsaturated carboxylic ester copolymers include ethylene/vinyl carboxylic ester copolymers such as ethylene/vinyl acetate (EVA) copolymers or ethylene/alkyl (meth)acrylates such as ethylene/ethyl acrylate (EEA) copolymers ( EAA) may be a copolymer. In some embodiments, (D) is present and is a polypropylene homopolymer. In some embodiments, (D) is present and is a polypropylene copolymer, which typically contains at least 60%, alternatively at least 70%, alternatively at least 80% by weight of propylene monomer units; at least 1% by weight of comonomer units; and up to 40%, alternatively up to 30%, alternatively up to 20% by weight of comonomer units. Other embodiments of (D), their properties and amounts, have been described above and hereinafter exemplified in Examples of the present invention.

Examples of polyethylene homopolymers useful as (D) are low density polyethylene (LDPE) (density 0.910 to 0.940 g/cm ³ ) and high density polyethylene (density up to 0.965 g/cm ³ ). Ethylene-based copolymers not prepared with molecular catalysts useful as (D) are prepared by copolymerizing ethylene and olefin functional comonomers with or without a ratio (molecular catalyst). Alternatively, (D) may also have a melt index (190°C, 2.16 kg) of from 2 to 60 g/10 min, alternatively from 5 to 40 g/10 min, as measured according to ASTM D1238-04.

optional components (E) to (O). Optionally, the peroxide-curable ethylene copolymer composition, and/or crosslinked ethylene/alpha-olefin copolymer prepared therefrom by curing such composition, contains zero, one or more additives and/or zero, It may contain one or more liquid aromatic or saturated hydrocarbons (LASH). When present, optional components (G) through (O) may independently represent >0.00 to 2.00%, alternatively 0.01 to 1.00% by weight of the peroxide-curable ethylene copolymer composition.

Optional Ingredients (E) Antioxidants. (E) the antioxidant serves to provide antioxidant properties to the peroxide-curable ethylene copolymer composition and/or peroxide-cured semiconductor product. Examples of suitable (E) include bis(4-(1-methyl-1-phenylethyl)phenyl)amine (eg NAUGARD 445); 2,2'-methylene-bis(4-methyl-6-t-butylphenol) (eg VANOX MBPC); 2,2′-thiobis(2-t-butyl-5-methylphenol (CAS No. 90-66-4, commercially available as LOWINOX TBM-6); 2,2′-thiobis(6-t-butyl- 4-methylphenol (CAS No. 90-66-4, commercially available as LOWINOX TBP-6): tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3; 5-triazine-2,4,6-trione (eg CYANOX 1790) Pentaerythritol tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl ) Propionate (e.g. IRGANOX 1010, CAS number 6683-19-8) 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2'-thiodiethane diyl esters (eg, IRGANOX 1035, CAS No. 41484-35-9); and distearyl thiodipropionate (“DSTDP”). In some embodiments, (E) is bis(4-(1- methyl-1-phenylethyl)phenyl)amine (eg, NAUGARD 445, commercially available from Addivant, Danbury, Conn.) (E) is 0.01 to 1.5 of the peroxide-curable ethylene copolymer composition. wt%, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt%.

Non-TAP Optional Ingredients (F) Adjuvants. (F) may be a compound having, on average, one or more -CH ₂ =CH ₂ functional groups per molecule. Examples of (F) are described above. In some embodiments, (F) is an unsaturated organophosphorus compound. In some embodiments (F) is alpha-methyl styrene dimer (AMSD) or diisopropenylbenzene (DIPB) or triallyl isocyanurate (TAIC). AMSD can be, for example, Nofmer MSD from NOF Corporation, also known as 2,4-diphenyl-4-methyl-1-pentene (CAS 6362-80-7). DIPB may be 1,3-diisopropenylbenzene (1,3-DIPB, CAS 3748-13-8, Sigma-Aldrich). When present, (F) may be at a concentration of from 0.05 to 1.0%, alternatively from 0.10 to 0.90%, alternatively from 0.1 to 0.60% by weight of the peroxide curable ethylene copolymer composition.

Optional Component (H) Hindered Amine Stabilizers. (H) is a compound that has a sterically hindered amino functional group and inhibits oxidative decomposition and, if present, can reduce acid-catalyzed decomposition of (C) organic peroxides. Examples of suitable (H) are butanedioic acid dimethyl ester, a polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS No. 65447-77-0, Commercially available is LOWILITE 62).

Optional Ingredients (I) Flame retardants. (I) reduces the flammability of cross-linked ethylene/alpha-olefin copolymers. Examples of flame retardants include organic halogen compounds including brominated flame retardants, inorganic synergist compounds such as antimony trioxide, organic phosphorus compounds, inorganic phosphorus compounds, metal hydrates, metal carbonates, and mixtures of two or more thereof.

Optional Component (J) Water tree retardant or electrical tree retardant. Water tree retardants are compounds that inhibit water treeing, a process by which polyolefins decompose when exposed to the combined effects of an electric field and humidity or moisture. Electrical tree retardants are compounds that inhibit electrical treeing, an electrical pre-breakdown process in solid electrical insulation due to partial electrical discharge. Electrotrilation can occur in the absence of water. Water trining and electrical trining are problems in electrical cables containing coated conductors, where the coating contains a polyolefin. (J) may be poly(ethylene glycol) (PEG).

Optional Component (K) Colorants. eg pigments or dyes such as titanium dioxide.

Ingredient (N) scorch retardant. Examples of scorch retardants are allyl containing compounds described in US 6277925B1, column 2, line 62, column 3, line 46.

Ingredient (O) filler. (O) The filler may be calcined clay, organic clay, carbon black, titanium oxide, or hydrophobized fumed silica such as that available commercially from Cabot Corporation under the trade name CAB-O-SIL. (O) The filler may have a flame retardant effect.

Other embodiments of components (E) to (O), their properties and amounts have been previously described, and in the case of components (E), (F), (H) and (J) are hereinafter exemplified in the examples of the present invention. . Components (E) and (H) through (K), and (N) can be used to impart one or more beneficial properties to a composition and/or product other than crosslink density. (G) PDMS fluid can be sprayed onto the pellets of the peroxide-curable ethylene copolymer composition to enhance its extrusion. (L) LASH is an additive that can be used to make, remove or deliver the peroxide-curable polymer composition or cross-linked ethylene/alpha-olefin copolymer. Components (E) to (O) are different compounds/substances derived from components (A) to (D) and from each other. Additives are typically not removed from cross-linked ethylene/alpha-olefin copolymers. (G) PDMS fluid and (L) LASH are chemically inert and can be volatile.

In addition, the peroxide-curable ethylene copolymer composition may further include a carrier resin, a corrosion inhibitor (eg, SnSO ₄ ), a lubricant, a processing aid, an antiblocking agent, an antistatic agent, a nucleating agent, a slip agent, a plasticizer, a tackifier, and a surfactant. , extender oils, acid scavengers, voltage stabilizers, antioxidants, and metal deactivators, each of one or more optional additives selected from 0.005 to 0.5% by weight.

To facilitate mixing of components (B) and (C) and optional components (D) to (O) with the component (A) cross-linkable ethylene/alpha-olefin copolymer, at least one component (B) and (D) and optional components (D) to (O) may be provided in the form of an additive master batch. The additive masterbatch may contain a dispersion of one or more of (B) to (C), and optionally (D) to (O) in a carrier resin. The carrier resin may be an EVA copolymer, an EAA copolymer or a poly(1-butene- co -ethylene) copolymer. The amount of carrier resin incorporated into the peroxide-curable ethylene copolymer composition may be 0 to <10 wt%, alternatively 0 wt%, alternatively >0 to 5 wt%. In the additive masterbatch, the carrier resin may be greater than or equal to 90% and less than 100% by weight of the additive masterbatch, together with (B) and (C), and any optional one or more of components (D) and (O). may be greater than 0% and up to 10% by weight of the total weight. In some embodiments, 1 to 20 parts by weight of the additive masterbatch may be mixed or blended with 99 to 80 parts by weight of (A) granules of the cross-linkable ethylene/alpha-olefin copolymer to provide a prepared mixture or blend thereof; It may then be pelletized according to the methods described herein to provide pellets. Thereafter, the pellets may be contacted with an appropriate amount of (C) organic peroxide to obtain the peroxide-curable ethylene copolymer composition. Alternatively, (C) the organic peroxide may be included in the additive masterbatch, and during its preparation and mixing with (A), the temperature of the additive masterbatch may be maintained below the 10-hour half-life temperature of (C).

A cross-linked ethylene/alpha-olefin copolymer. The crosslinked ethylene/alpha-olefin copolymer contains a mesh polyolefin resin containing CC bond crosslinks formed during curing of the peroxide-curable ethylene copolymer composition. The networked polyolefin resin comprises the product of coupling (A) a cross-linkable ethylene/alpha-olefin copolymer or, if present, (D) a supplemental polymer. Ethylene/alpha-olefin copolymers or, if present, other approaches for crosslinking (D), such as radiation crosslinking, and as described above, wherein (A) and/or (D) contain hydrolyzable silyl groups. In embodiments, moisture induced cross-linking may also be used. The peroxide-cured ethylene/alpha-olefin copolymer may also contain (C) a by-product obtained by curing the alcohol product of the reaction of an organic peroxide. When the peroxide-curable ethylene copolymer composition further contains one or more optional components (D) to (O), the cross-linked ethylene/alpha-olefin copolymer comprises any one or more optional components (D) to (O). O), or one or more reaction products formed therefrom during curing of the peroxide-curable ethylene copolymer composition. Any (L) lash and any other volatile compounds (e.g., unreacted comonomers) are removed from the cross-linked ethylene/alpha-olefin copolymer so that it is independently free of LASH and other volatile compounds or greater than 1 each A cross-linked ethylene/alpha-olefin copolymer containing less than weight percent. Such removal may be accomplished by any suitable means such as decantation, devolatilization, distillation, evaporation, filtration, sparging with an inert gas (eg dry N ₂ gas) and stripping. there is. The cross-linked ethylene/alpha-olefin copolymer can exist in either a segmented solid form or a continuous form. Divided solid forms may include granules, pellets, powders or combinations of any two or more of these. Continuous forms can be molded parts (eg hollow molded parts) or extruded molded parts (eg coated conductors or cables).

coated conductors. The coated conductor may be an insulated electrical/optical conductor, which may be an insulated electrical conductor, an insulated optical conductor, or an insulated electro-optical conductor. Insulated light conductors may include coated optical fibers and/or fiber optic cables for use in data transmission applications. Insulated electrical conductors may include coated metal wires and/or electrical cables, including power cables, for use in low voltage, medium voltage, high voltage and extra high voltage power transmission applications. Insulated electro-optic conductors may include coated combinations of optical fibers and metal wires for use in both data transmission and power transmission applications. “Wire” means a single strand or filament of a conductive metal such as copper or aluminum, or a single strand or filament of optical fiber. "Cable" and "power cable" are synonymous and mean an insulated conductor comprising at least one wire or optical fiber, or a combination thereof, which is enclosed within a sheath, which may be called a sheath, jacket (protective outer jacket), or coating. Located. When the insulated conductor includes a wire, it may be referred to as an insulated electrical conductor. If it includes an optical fiber, it may be called an insulated light conductor. Insulated electrical conductors can be designed and manufactured for use in medium, high, or extra-high voltage applications. Examples of suitable cable designs are US Pat. Nos. 5,246,783; U.S. Patent No. 6,496,629; and U.S. Patent No. 6,714,707.

An insulated electrical/optical conductor may include a conductor core and an outer single- or multi-layer cladding disposed therearound to protect and insulate the conductor core from the external environment. The conductor core may consist of one or more metal wires, one or more optical fibers, or a combination thereof. When the conductor core includes two or more metal wires and/or optical fibers, the metal wires may be subdivided into separate wire bundles, and the optical fibers may be subdivided into separate optical fiber bundles. Each wire or fiber within the conductor core, whether bundled or not, may be individually coated with an insulating layer, and/or separate bundles (bundles) may be coated with an insulating layer. A single- or multi-layer covering (e.g., single- or multi-layer coating or covering) is primarily intended to protect against sunlight, water, heat, oxygen, other conductive substances (e.g., to prevent short circuits), and/or other corrosive substances (e.g., chemical fumes). It functions to protect or insulate the conductor core from the external environment.

Single-layer or multi-layer coverings from one insulated electrical/optical conductor to the next may be configured differently depending on each intended use. For example, when viewed in cross section, a multi-layer coating of an insulated electrical conductor may consist of the following components sequentially from the innermost layer to the outermost layer: an inner semiconducting layer, a cross-linked ethylene/alpha-olefin copolymer ( A crosslinked polyolefin insulating layer, an outer semiconductive layer, a metal shield and a protective cover comprising the crosslinked product of the present invention). The layer and covering are continuous in a circumferential plane and in a common axial plane (longitudinal). The metal shield (ground) is continuous in the common axis plane, continuous (layer) or discontinuous (tape or wire) in the circumferential plane. Depending on the intended application, multilayer claddings for insulated light conductors may omit the semiconductor layer and/or metal shield, but to prevent crosstalk between optical fibers and/or reinforcing materials such as polymer fibers or bundles thereof. Excessive bending that causes breakage of the optical fiber can be prevented by including a light blocking material. The outer semiconductive layer, if present, may consist of a peroxide-crosslinked semiconductor product capable of stripping from the crosslinked polyolefin layer.

How to conduct electricity. The method of conducting electricity of the present invention may use a coated conductor of the present invention, including the insulated electrical conductor embodiments or the insulated electro-optical conductor embodiments of the immediately preceding paragraph.

Advantageously, the present inventors find that the cross-linked ethylene/alpha-olefin copolymer product (cross-linked product of the present invention) is suitable for use as a single-layer coating or a multi-layer coating cross-linked polyolefin insulating layer of the insulated electrical/optical conductor. It has been found to exhibit sufficient flexibility and satisfactory thermal or oxidative stability. The peroxide-curable ethylene copolymer composition (composition of the present invention) is useful for preparing the crosslinked product of the present invention. The crosslinked product of the present invention obtained after curing of the composition of the present invention has an improved (i.e., increased) TER (after 7 days or 28 days) compared to the comparative composition without TAP and the comparative crosslinked product without TAP made therefrom. after 136° C.), enhanced (ie, increased) OIT (O ₂ , 185° C.), and/or unchanged or less than 3-fold reduced (ie, <3x increased), alternatively unchanged or 2-fold DF (130° C., 60 Hz, 2 kV) reduced to less than (i.e., <2x increased). In some embodiments, the cross-linked ethylene/alpha-olefin copolymer product is further defined by any one of the following limitations (i) to (iii): (i) at least 20%, alternatively at least 40%, alternatively typically at least 50%, alternatively at least 60%, alternatively at least 65%; and a TER (136° C. after 7 days or 28 days) of at most 200%, alternatively at most 150%, alternatively at most 120%, alternatively at most 110%, alternatively at most 100%; (ii) at least 6 minutes, alternatively at least 10 minutes, alternatively at least 20 minutes, alternatively at least 30 minutes; and an OIT (O ₂ , 185° C.) of at most 60 minutes, alternatively at most 50 minutes, alternatively at most 45 minutes; and (iii) both (i) and (ii). In some embodiments, the crosslinked ethylene/alpha-olefin copolymer product has 0.05% to 1.10%, alternatively 0.10% to 1.10%, alternatively 0.50% to 1.10% of (iv) DF (130° C., 60 Hz , 2 kV). In some embodiments, a composition of the present invention features a cross-linked product of the present invention prepared therefrom, wherein the cross-linked product of the present invention is characterized by any one of limitations (i) through (iv) described above. In contrast, a non-inventive comparative crosslinked product made from a non-inventive comparative peroxide-curable ethylene copolymer composition identical in composition to a composition of the present invention, provided that the comparative composition is free of (and does not contain) triallyl phosphate. a TER (136° C. after 7 days or 28 days) of less than 50%, alternatively less than 40%, alternatively less than 30%, alternatively less than 20%; and/or an OIT (O ₂ , 185° C.) of up to 10 minutes, alternatively up to 5 minutes. The insulated electrical/optical conductors of the present invention are useful in data transmission applications and/or power transmission applications including low, medium, high and extra-high voltage applications.

Compositions of the present invention (eg according to aspects 1 to 7) and products of the present invention (eg according to aspects 9 or 11) are suitable for use in medium voltage, high voltage and extra high voltage electrical cables, such as medium voltage electrical cables. It is useful in a number of applications as a component of coatings of coated conductors (eg, insulated electrical conductors), including coated wires or coated cables for use in the electrical or telecommunications industry.

Test samples of embodiments of the unfilled and filled compositions may be prepared as individually compression molded plaques. The mechanical properties of these compositions can be characterized using test specimens cut from compression molded plaques.

Olefin polymerization catalysts include Ziegler-Natta catalysts, chromium catalysts and molecular catalysts. Ziegler-Natta (ZN), such as TiCl ₄ /MgCl ₂ , and chromium catalysts, such as chromium oxide/silica gel, are heterogeneous in that their catalytic sites are not derived from a single molecular species. Heterogeneous catalysts produce polyolefins with a broad molecular weight distribution (MWD) and a broad chemical composition distribution (CCD). Molecular catalysts are theoretically homogeneous in that they have a single catalytic site derived from a ligand-metal complex molecule with a defined ligand and structure. As a result, molecular catalysts produce polyolefins with narrow CCD and narrow MWD, but in practice fall short of the theoretical limit of Mw/Mn = 2. Metallocenes are molecular catalysts containing unsubstituted cyclopentadienyl ligands (Cp). Post-metallocenes are derivatives of metallocenes that contain one or more substituted CP ligands, such as constrained geometry catalysts, or are non-sandwich complexes. Examples of post-metallocene catalysts are bis phenylphenoxy catalysts, constrained geometry catalysts, imino-amido type catalysts, pyridyl-amide catalysts, imino-enamido catalysts, aminotroponymineto catalysts, amino doquinoline catalysts, bis(phenoxy-imine) catalysts and phosphinimide catalysts.

Method for preparing the composition. A typical compounding temperature of 150°C, in a Banbury compounder using a rotor speed of 60 to 65 revolutions per minute (rpm), or an extrusion temperature of 160°C or higher (e.g., 200°C) and 200 rpm In a ZKS twin-screw extruder using a screw speed of , the components of the peroxide-curable polyolefin composition (of the comparative example or the inventive example) are melt blended. For lab scale procedures, batch mixers and single screw extruders are used for melt blending and pelletization. The peroxide and other liquid additives are immersed into the pellets containing the blended additives at 50° C. to 80° C. for 6 to 24 hours. Manufacturing method 1 below is an example of a laboratory scale procedure.

Compression Molded Plaque Manufacturing Method: The crosslinked product is formed into plaques of different thicknesses (e.g., 50 mils (1.3 mm) thick plaques for dielectric modulus testing) according to the test procedure using the peroxide-curable ethylene copolymer composition under the following conditions. ), it can be prepared in the form of compression molded plaques: 500 psi (3.4 MPa) at 125° C. for 3 minutes, then 2500 psi (17 MPa) at 180° C. for 20 minutes, then 30° C. at 2500 psi pressure. Cooling to °C gives the form of compression molded plaques of the cross-linked product.

Density Test Method: (for testing solid plastics in liquids other than water, such as liquid 2-propanol) according to ASTM D792-13, Method B , Standard Test Method for Density and Specific Gravity (Relative Density) of Plastics by Displacement Measured. Results are reported in grams per cubic centimeter (g/cm ³ ).

Dissipation factor test method 1 for DF (130 ℃, 60 Hz, 2 kV): Measurements are made according to ASTM D150-11, Standard Test Method for Alternating Current Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulation (herein excluding differences described in ). Performed on cross-linked circular specimens cut from plaques 50 mil (1.3 mm) thick. Plaques were degassed in a vacuum oven at 60° C. for 5 days. A GUILDLINE high voltage capacitance bridge (model 9920A) was used with a TETTEX specimen holder and a TETTEX AG instrument temperature control unit. Samples were tested at 60 Hz and 2 kV and stressed at 130 °C (alternative temperatures, 25 °C, 40 °C or 90 °C). The same method can be used to measure the dielectric constant. 1 day = 24 hours. 1 hour = 60 minutes. 1 minute = 60 seconds

Dielectric coefficient test method 2 for DF (100 ℃, 50 Hz, 2 kV): Measured by QS87 bridge equipped with a power supply and electrode system of 10 kV immersed in silicone oil in an oven: (1) cross-linked plaques at 70 Degassed for one day at °C. (2) When the temperature of the electrode rises to about 100° C., the degassed plaque is put into the electrode. (3) At 100°C, increase the voltage to 2kV (first), then to 4kV, and then to 2kV (second). (4) Measure the DF at each stress level and record the DF at 4 kV and the second 2 kV, and the corresponding electrode temperature.

Flexural Modulus (2% Secant) Test Method: Measured at 23°C according to ASTM D790-15e2 Standard Test Method for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials , with crosshead position and 125 mil (3.18 mm) Thickness is measured at a strain of 2% and 0.05 inches per minute (0.127 cm/min) in compression molded specimens, and is expressed in pounds per square inch (psi) or equivalent megapascals (MPa).

Glass Transition Temperature (Tg) and Melting Point Test Method: Measured by Differential Scanning Calorimetry (DSC) according to ASTM 3418-15, Standard Test Method for Transition Temperature and Enthalpy of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry , expressed in degrees Celsius (°C).

Melt Index I ₂ Test Method: Melt Index I ₂ for ethylene-based (co)polymers under conditions of 190°C/2.16 kilograms (kg) (previously known as “Condition E” and also known as I ₂ ), ASTM D1238 -04, measured according to the Standard Test Method for Melt Flow Rate of Thermoplastics by an Extrusion Platometer . Results are reported in grams eluted per 10 minutes (g/10 minutes) or in equivalent units of 1.0 decigrams per minute (dg/1 minute). 10.0 dg = 1.00 g. Melt index is inversely proportional to the weight average molecular weight of polyethylene, although the inverse is not linear. Therefore, the higher the molecular weight, the lower the melt index.

Oxidation induction time test method for OIT (O ₂ 185°C): time difference required to initiate the oxidation reaction of a test sample of a crosslinked polyolefin composition prepared by a compression molding plaque manufacturing method under a molecular oxygen atmosphere at 185°C It is measured by scanning calorimetry (DSC). A TA Instruments Thermal Analysis Q-1000 DSC instrument equipped with a modular DSC standard cell is used. A test sample of approximately 2 mg was cut into thin slices using a razor blade. Place the sliced test sample in an open aluminum DSC pan. Equilibrate the pan/contents at 60° C. for 5 minutes under nitrogen gas flowing at 50 milliliters per minute (mL/min). Then, the temperature was raised to 185 °C at 20 °C per minute under nitrogen gas and maintained at 185 °C for 5 minutes under nitrogen. The gas was then switched to molecular oxygen at a flow rate of 50 mL per minute, from when the oxygen gas was turned on (time 0) until the onset of a significant exothermic peak in the DSC (oxidation induction time, or OIT (O ₂ , 185 °C)). The elapsed time of was recorded The longer the elapsed time to OIT (O ₂ , 185° C.), the more resistant the test sample is to oxidative heat aging.

Tensile Elongation Retained Test Method for TER (136°C after 7 days or 28 days): crosslinked and heat-aged (oven) samples as well as crosslinked according to ASTM D638 and UL 1581/2556 The tensile elongation (strain at break) of the bonded but unaged samples was measured. This method used Type IV dog bone-shaped specimens with a displacement rate of 20 inches (51 cm) per minute and a nominal thickness of 70 mils (1.8 mm). Measurements were repeated 4 or 5 times in each condition and the average was obtained. Tensile properties were measured on unaged crosslinked seams (i.e., held at room temperature of 23° C. after compression molding) and heat aged crosslinked specimens aged at 136° C. for 7 days or 28 days. Heat aging is performed using a Type II ASTM D5423-93 Testing Mechanical Convection Oven. The tensile retention elongation (TER) (7 days or 28 days, 136° C.) of a heat-aged specimen is expressed as a percentage of the tensile elongation value of the corresponding unaged specimen.

Example

Component (A1): An ethylene-1-octene copolymer characterized by: a density of 0.872 g/cm ³ measured according to ASTM D792; Melt Index (190°C, 2.16 kg) measured according to ASTM D1238 is 4.8 g/10 min; Flexural modulus (2% sec) of 1570 psi (10.8 MPa) measured according to ASTM D790-15e2; and a glass transition temperature (Tg) of -53°C as measured by differential scanning calorimetry (DSC) according to ASTM 3418-15. It was obtained commercially as Developmental XUS 38660.00 Polyolefin Elastomer from The Dow Chemical Company (Midland, Michigan, USA).

Component (A2): An ethylene/propylene/ENB terpolymer having the following characteristics: a density of 0.88 g/cm ³ measured according to ASTM D792; ASTM D3900-17 ( Standard Test Method for Rubber - Ethylene-Propylene Copolymers ( EPM ) and Ethylene-Propylene- Dienes an ethylene content determined according to infrared spectroscopy of the ethylene units of the terpolymer (EPDM) of 67% by weight; Measured according to ASTM D6047-17 ( Standard Test Method for Rubber, Raw Material Determination of 5-Ethylidene Norbornene (ENB) or Dicyclopentadiene (DCPD) in Ethylene - Propylene- Diene ( EPDM ) Terpolymer ) ENB (5-ethylidene-2-norbornene) content is 4.9% by weight; ASTM D1646-15 ( Rubber - Standard Test Method for Viscosity, Stress Relaxation and Pre- Vulcanization Properties (Mooney Viscometer) ) has a Mooney Viscosity (ML1+4 at 125°C) of 60. It is available as NORDEL IP 4760 from The Dow Chemical Company.

Component (B1): Triallyl phosphate (TAP) with a purity greater than 96% obtained commercially from TCI America, Portland, Oregon, USA.

Component (C1): Dicumyl peroxide commercially obtained as PERKADOX BC-FF from AkzoNobel.

Component (C2): 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, available as LUPEROX® 101 from Arkema.

Component (D1): A polypropylene homopolymer characterized by: a melt flow (230° C., 2.16 kg) of 1.8 g/10 min measured according to ASTM D1238; Flexural modulus (0.05 in/min, 1% sec) of 190,000 psi (1,310 MPa) measured per ASTM D790A. It was obtained commercially from Braskem as Braskem FF018F.

Ingredient (E1): 2,2'-thiobis(2-t-butyl-5-methylphenol (CAS No. 90-66-4). Obtained commercially as LOWINOX TBM-6 from Addivant.

Component (F1): 2,4-diphenyl-4-methyl-1-pentene (AMSD). It was obtained commercially as Nofmer MSD from NOF Corporation (White Plains, New York, USA).

Component (H1): 1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl] (1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N',N"-dibutyl- N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-. Obtained commercially as SABOSTAB UV 119 from SABO S.p.A., Italy.

Component (J1): PEG 20000, a poly(ethylene glycol) with an average molecular weight (M _n ) of 20000 g/mol, obtained commercially from Clariant, Charlotte, NC, USA.

Comparative Examples 1 and 2 (CE1 and CE2): See Preparation Method 1.

Comparative Example 3 (CE3): See Preparation Method 2.

Inventive Examples 1 to 4 (IE1 to IE4): See Manufacturing Method 1.

Inventive Example 5 (IE5): See Preparation Method 2 below.

Production method 1: (C1) was melted at 60°C, and (F1) was mixed with the obtained melt at a weight/weight ratio (C1)/(F1) of 5:1 to obtain a molten mixture. (A1), (D1), if any, (E1), (H1) and (J1) were manually mixed in a container to obtain a solid mixture. The solid mixture (after loading) was mixed at 190° C. in a Brabender batch mixer with a capacity of 420 cm ³ with a cam rotor at 40 revolutions per minute (rpm) for 5 minutes to obtain a solid mixture. The mixture was removed from the mixer, the mixture was cold pressed into a thin sheet and then the sheet was cut into strips. The strip was cured in a freezer, and then the cured strip was fed into a pelletizer to obtain pellets. The pellets are heated in a glass jar at 50° C. for 2 hours, then the heated pellets are sprayed into the C1)/(F1) molten mixture, and in the case of IE1 to IE4 (B1) also sprayed to obtain peroxide curing properties in the glass jar. An ethylene copolymer composition was obtained. ((B1) was not used in the case of CE1 or CE2). The glass jar was inverted to mix the contents at room temperature for 10 minutes, then the jar and contents were placed in an oven at 50° C. for 16 hours. The obtained contents were mixed for 10 minutes (after loading) in a Brabender mixing vessel with a capacity of 420 cm ³ equipped with a cam rotor at 30 rpm at 120° C. A composite composition was obtained. A sample was removed from the vessel, the sample taken out was cold pressed or compression molded, and the cold compression or compression molded sample was characterized. The composition and characterization of the peroxide-curable ethylene copolymer compositions of IE1 to IE4 and CE1 and CE2 are shown in Table 1 below.

Cold pressed samples of the composition were compression molded under conditions that prevented significant crosslinking and tested for melt rheological properties. Conditions that would prevent significant cross-linking were pressurization at 120°C to 500 PSI (3.5 MPa) for 3 minutes followed by 120°C to 2500 PSI (to 17 MPa) for 3 minutes followed by cooling to 30°C under the latter pressure; , to open the press and take out the obtained compression molded plaque. Another sample of the composition was compression molded under complete cross-linking conditions to prepare specimens of different dimensions (see Method of Making Compression Molded Plaques above), and the specimens were tested for electrical and mechanical properties. Data are shown in Table 1 below.

Manufacturing Method 2: Equilibrate Haake mixer at 100°C. Components A2, B1 (if present), and C2 are then added to the mixer. Mix for 4 minutes at 100° C. at 35 revolutions per minute (rpm) to obtain the final polymer blend. The blend is cold pressed into an initial sheet according to the cold press method below. The initial sheet is subjected to two roll milling at 75° C. to obtain a final sheet of 1 mm thickness. See Table 2.

Cold press samples of Manufacturing Method 2 were compression molded under conditions that prevented significant crosslinking and tested for melt rheological properties. Conditions for preventing significant cross-linking are compression at 120°C at 10 MPa for 2 minutes, followed by compression at 180°C at 10 MPa for 15 minutes, followed by cooling to 30°C under a pressure of 10 MPa, followed by opening the press and the obtained compression The cosmetic plaque was taken out. The electrical properties of the specimens were tested. Data are shown in Table 2 below.

Table 1: Composition and test results for the examples ("0" means 0.00)

Table 2. Composition and test results for the examples ("0" means 0.00)

^* may not add to 100.00 due to rounding. ^** N/M = Not measured. ^ repeated CE2. (1) Oxidation induction time when heated in an oxygen atmosphere at 185 °C (min), (2) Tensile retention elongation (%) after heating at 136 °C for (a) 7 days or (b) 28 days, (3) at one end Apparent flexibility, (4) 130°C, 60 Hz, Dielectric coefficient (%) tested at 2 kV (Table 1) or 100 °C, 50 Hz, 4 kV or 2 kV (Table 2).

The data in Table 1 shows that the cross-linked ethylene/alpha-olefin copolymer products prepared from each of the peroxide-curable ethylene copolymer compositions (Examples IE1 to IE4) have cross-linked polyolefin insulation of multilayer coatings of insulated electrical/optical conductors. It exhibits sufficient thermal and/or oxidative stability for use as a layer. Examples IE2 to IE4 show improved (i.e., increased) TER (7 days or 28 days, 136° C.), improved (i.e., increased) OIT (O ₂ , 185 °C) and unchanged or less than 2-fold reduced (ie <2x increased) DF (130 °C, 60 Hz, 2 kV). Example IE1 is characterized by improved (ie, increased) OIT (O ₂ , 185° C.) and less than 2-fold reduced (ie, <2× increased) DF (130° C., 60 Hz, 2 kV); It is expected to have an improved (i.e., increased) TER (7 days or 28 days, 136° C.) compared to Comparative Example CE1 without the respective TAP. Compare IE1 to CE1 and compare IE2 to IE4 to CE2. Compositions CE1 and CE2 were compositionally identical to compositions IE1 or IE2 to IE4, respectively, except that compositions IE1 to IE4 contained triallyl phosphate, while compositions CE1 and CE2 lacked triallyl phosphate.

As a result of comparing CE3 and IE5 in Table 2, triallyl phosphate also improved DF (100 ° C, 50 Hz, 4 kV or 100 ° C, 50 Hz, 2 kV) in crosslinked ethylene / alpha-olefin / diene terpolymers. (ie, reduced), the same was true for (C2), an organic peroxide different from (C1).

Claims (15)

As a peroxide-curable ethylene copolymer composition,
prepared by a process comprising copolymerizing ethylene and an alpha-olefin comonomer, and optionally another comonomer selected from a non-conjugated diene and a second alpha-olefin, in the presence of a molecular catalyst useful therefor, 58.00 to 99.90% by weight of (A) a cross-linkable ethylene/alpha-olefin copolymer ("copolymer (A)" or "component (A)");
0.050 to 0.949% by weight of (B) triallyl phosphate (TAP);
0.050 to 5.00% by weight of (C) an organic peroxide; and
0.00 to 40% by weight of (D) a supplemental polymer selected from ethylene/unsaturated carboxylic acid ester copolymers, polyethylene homopolymers, non-(molecular catalyst) type ethylene/alpha-olefin copolymers and propylene-based polymers,
provided that the total weight of component (A) and component (D) is 80.00 to 99.90% by weight; wherein all weight percentages are based on the total weight of the peroxide curable ethylene copolymer composition, and the total weight of the peroxide curable ethylene copolymer composition is 100.0 weight %. The composition of claim 1 , further described by any one of the following limitations (i) to (ii):
(i) the alpha-olefin comonomer is a (C ₃ -C ₂₀ ) alpha-olefin, and the (A) ethylene/alpha-olefin copolymer has the following properties (a) to (c): (a1) ASTM Flexural modulus (2% secant) of >0 to 40,000 psi (>0 to 278 MPa) measured according to D790-15e2 and/or (a2) 0.850 to 0.930 grams per cubic centimeter (g/cm) measured according to ASTM D792 ³ ), (b) a glass transition temperature (Tg) of -130 ° C to -20 ° C measured by differential scanning calorimetry (DSC) according to ASTM 3418-15, and (c) according to ASTM D1238-04 Ethylene-(C ₃ -C ₂₀ ) alpha characterized by at least one of a measured melt index of 0.5 decigrams per minute (dg/min) to 50 dg/min (190° C., 2.16 kilograms (kg), “I ₂ ”). -is an olefin copolymer; or
(ii) the alpha-olefin comonomer is propylene and the other comonomer is used and is a non-conjugated (C ₆ -C ₂₀ ) diene, and the (A) cross-linkable ethylene/alpha-olefin copolymer has the following properties: (a) to (c): (a1) a flexural modulus (2% secant) of >0 to 20,000 psi (>0 to 138 MPa) measured according to ASTM D790-15e2 and/or (a2) measured according to ASTM D792 density in grams per cubic centimeter (g/cm ³ ) between 0.850 and 0.910; (b) a glass transition temperature (Tg) of -130°C to -20°C as measured by differential scanning calorimetry (DSC) according to ASTM 3418-15; and (c) a melt index (190° C., 2.16 kilograms (kg), “I ₂ ”) of from 0.1 decigrams per minute (dg/min) to 50 dg/min measured according to ASTM D1238-04. is an ethylene-propylene-(C ₆ -C ₂₀ ) diene copolymer (EPDM). ◈Claim 3 was abandoned when the registration fee was paid.◈ The composition according to claim 1 or 2, further described by any one of the following limitations (i) to (iv):
(i) the (A) cross-linkable ethylene/alpha-olefin copolymer is 90 to 99% by weight of the peroxide-curable ethylene copolymer, and the peroxide-curable ethylene copolymer composition does not contain the (D) supplemental polymer; none (deficient);
(ii) the (A) cross-linkable ethylene/alpha-olefin copolymer is 58.00 to 90.00 weight percent and the (D) supplemental polymer is 40.0 to 1.0 weight percent of the peroxide-curable ethylene copolymer composition;
(iii) said (D) supplemental polymer is a polypropylene homopolymer; and
(iv) is both (ii) and (iii). ◈Claim 4 was abandoned when the registration fee was paid.◈ 3. The method of claims 1 or 2, further described by any one of the following limitations (i) to (iv), wherein all weight percentages are based on the total weight of the peroxide-curable ethylene copolymer composition: Composition to be:
(i) 0.090 to 0.940 weight percent of (B) triallyl phosphate (TAP);
(ii) 0.100 to 0.900% by weight of (B) triallyl phosphate (TAP);
(iii) 0.19 to 0.849 weight percent of (B) triallyl phosphate (TAP);
(iv) 0.200 to 0.800% by weight of (B) triallyl phosphate (TAP). ◈Claim 5 was abandoned when the registration fee was paid.◈ The composition according to claim 1 or 2, further described by the following limitations (i) or (ii):
(i) the total amount of components (A) to (D) is 100% by weight thereof; or
(ii) the total amount of components (A) to (D) is less than 100% by weight thereof, and the peroxide-curable ethylene copolymer composition comprises (E) an antioxidant; (F) an adjuvant other than TAP; (G) polydimethylsiloxane (PDMS) fluid; (H) hindered amine stabilizers; (I) flame retardants; (J) tree retardants; (K) colorants; (L) liquid aromatic or saturated hydrocarbons (LASH); (M) methyl radical scavengers; (N) scorch retardants; and (O) a filler. A method for producing the peroxide-curable ethylene copolymer composition according to claim 1 or 2,
wherein said method comprises contacting effective amounts of components (A) through (C) with optional optional components (D) through (O) to produce said peroxide-curable ethylene copolymer composition. A crosslinked ethylene/alpha-olefin copolymer product, which is a product obtained by curing the peroxide-curable ethylene copolymer composition of claim 1 or 2. An article of manufacture comprising a shaped form of the crosslinked ethylene/alpha-olefin copolymer product of claim 7 . ◈Claim 9 was abandoned when the registration fee was paid.◈ A coated conductor comprising a conductive core and an insulating layer at least partially covering the conductive core, wherein at least a portion of the insulating layer comprises the cross-linked ethylene/alpha-olefin copolymer product of claim 7 . ◈Claim 10 was abandoned when the registration fee was paid.◈ As a method of conducting electricity,
The method comprising applying a voltage across the conductive core of the coated conductor of claim 9 to cause a flow of electricity through the conductive core. delete delete delete delete delete